Trisazo dyestuff and process of preparing the same



Patented June 13, 1933 "waist STATES PATENT orricE IVAN GUBELMANN, OF SOUTH MILWAUKEE, ANDARTH-IIR It. ivrunrnnor MILWAUKEE, wIsooNsIN, ASSIGNORS, BY MESNE ASSIGNMENTS, TO n. I. no FONT DE NnMoUns &

OOMPA Y, A CORPORATION OF DELAWARE TRIsAzO nYEsTurF ANnrnoOEss OFrnErAnING THE SAME No Drawing, Application filed July 6,

, We have foundthat dyestuffs satisfying I these qualifications may be. obtained by d1- san tizing an aryl-amine. of the benzene or naphthalene serles and coupling the same to a diallfoxy-aniline .havingthe position para to the amino group free, rediazotizing and coupling to Cleves acid or to another dialirony-aniline molecule having a free para position, rediazotizing and finally coupling to a 2-an1ino-5-naphthol-7-sulfonic acid compound. Ifdesired, the sequenceofthe second and third components maybe interchanged. 1 i I M Our novel dyestuffs have thefigeneral formula} wherein R is an aryl radical of thebenzene or naphthalene series, preferably containing one or more snlfonic acid groups, and optionally containing other subst tuents, such as alkyl, halogen, hydroxy, alkoxygroups n and the like; least one of the groups R and R is a dialkoXy-aniline radical having;

a free para position While the other one is Cleves acid radical or another dialkoxy aniline radical of the type above defined; u, and wherein R stands for a.-2-ainino-5- naphthol-7-sulfonic acid compound, such as.

21-amino-5-naphtholfisulfonic acid. itself or its lf-alkyl, aryl, aralkyl, acidyl. or azole derivatives. @ur novel dyestulfsidye cotton directly in blue shades of excellent fastness to light. They also dye silk and regenerated cellulose fibers. The shades obtained by our novel dyestuffs on cotton or silk are con-" siderably greener than those obtainable by the analogous trisazo dyestuffs having as 1 second. or third component an a-naphthyL aniline This effect is rather surharnine r due in lieu of our dimethoxy-u 1931. Serial NO. 549,094.

derivatives, such. as aniline, o-toludine, p-xyhd1ne, or .ClBSlCllIlG, when used as middle components in trlsazo dyestuffs of the above. type, give shades more toward the. violet than the a-naphthylaminel residues.

The following examples Will serve further to illustrate our invention, butit should be understood that the same are merely illustrative, notlimitative. The parts given are parts by Weight. I

. I 1 Example 1 p 273 parts of the monosodium salt of aniline-2,5-disulfonic acid, dissolved in 3000 parts of Water, and cooled to 0., are diaz otized with 348 partsof hydrochloric acid Be.) and 69 parts of sodium nitrite. To the resulting diazo solution are added 245 parts of 1,7-C'leves acid (sodium salt),

dissolved in i,500 parts of Water. The mixpling is completed. The amino-disazo body is now further diazotized by adding 60 parts of hydrochloric acid (20 B.) and 69 parts of sodium nitrite. The diaZo-disazo mass is now added to 31.5 parts of 2-phenylamino-5- naphthol-7-sulfonic acid dissolved in a miture of 5000 parts of water, and 7 38 parts of an aqueous ammonia solution containing 250 grams ammonia per liter. After the formation of the dyestuff, the mix tureis heated to 85 0.; 1,600 parts of common salt (NaGl) are added to salt out the dyestuff, and the latter is filtered. off and dried. V I I The dyestuff thus produceddyes cotton a greenish blue shade; it dissolves in Water to give a blnesolution, and in concentrated *sulfuricacid to give a deep navy blue solution.

In the form of its free acid it corresponds most probably to the following formula:

Ewample 2 325 parts of the monosodium salt of 2- naphthylamine-4,8-disulfonic acid are dissolved in 5000 parts of Water, and 348 parts of hydrochloric acid (20 B.) are added. The mixture is cooled to 5 (3., and diazotized with 69 parts of sodium nitrite. To the diazo mixture thus obtained there is added 160 parts of 2,5-dimethoxy-aniline dis solved in 3000 parts of Water and 17 parts of hydrochloric acid (20 B.). The mass is stirred until coupling is completed; heated to 80 (1; and salted out with 1275 parts of common salt. The precipitated amino azo compound is filtered oil, pas ed up with 10000 parts of Water, and dissolved with 40 parts of caustic soda. 09 parts of sodium nitrite are now added and diazotization e1- fected by the rapid addition of 46 1 parts of hydrochloric acid (20 1%.). The mass is stirred until diazotization is complete; the insoluble diazo-azo body is filtered oil", and

pasted up with 8000 parts of ice and Water..

To the suspension thus obtained a solution of 245 parts of mixed Cleves acid (sodium salt), dissolved in 2000 parts of water is now added, and the mixture is stirred until coupling'is complete. The resulting mixture is made slightly alkaline with 53 parts of soda ash; 69 parts of sodium nitrite are added, and diazotization is eliected by the rapid addition of 3&8 parts oi hydrochloric acid (20 The mass is now stirred un-- til diazotization is complete and added to a solution of 239 parts of 2-amino-5-naphthol 7-sulfonic acid dissolved in 4000 parts of water containing 40 parts oi. caustic soda and 212 parts of soda ash. The finished coupling mass is now heated to 90 (1., salted out with. 2550 parts of common salt, filtered off and dried.

The dyestuft thus produced dyes cotton navy blue shades and is soluble in concentrated sulfuric acid to a deep greenish blue. In the form of its free acid, it corresponds most probably to the following formula E wample 3 273 parts of the monosodium salt of aniline-2,5-disultonic' acid are dissolved in 3000 parts of Water, and 348 parts of hydrochloric acid (20 Be.) are added. The mixture is cooled to 5 (1, and diazotized by the addition of 69 parts of sodium nitrite. 190 parts of 2,5-dimethoxy-aniline-hydrochloride are dissolved in 3000 par s of water; added to the above diazo mixture; and stirred until the formation of the monoazo compound is completed. The coupling mass is heated to 85 C., 1000 parts of common salt are added, and the amino-azo body is filtered off, and dissolved in 2000 parts of water containing 40 parts of sodium hydroxide. 69 parts of sodium nitrite are noW added and diazotization effected by the rapid addition of 348 parts of hydrochloric acid (20 B.), and stirring until diazotization is complete. 190 parts of 2,5-dimethoxy-anilinehydrochloride are dissolved in 4000 parts of Water, and added to the above diaZo mixture; the mass is neutralized with 280 parts of sodium acetate (crystals), and stirred until coupling is complete. The insoluble amino-disazo body is filtered off; dissolved in 15000 parts of Water containing are parts of caustic soda, and diazotized by the addition of 69 parts of sodium nitrite and e64 parts of hydrochloric acid (20 Be). The mass is stirred until diazotisation is complete, added to a mixture of 315 parts of 2-phenylamino-5-naphthol-7-sulfonic acid, in 5000 parts of Water, 40 parts of caustic soda, and 240 parts of aqueous NILOH (25% NH and stirred until coupling is complete. The dyestufi is isolated by heating to 80 0., salting out with 2000 parts of common salt, filtering and drying.

This product dyes cotton a grayish-blue shade and is soluble in concentrated H l to a deep navy blue color. In the form of coupled to 239 parts of 2-amino-5-naphtholblue solution.

its free acid, :it corresponds most probably to the following formula: 9

Emample 4 If instead of coupling the diazo-disazo body mentioned in Example 1 to 2-pl1enyl-f amino-5-naphthol-7-sulfonic acid, it is 7-sulfonic aciddissolvedin 1000 parts of sodium carbonate and 5000 parts of Water, one

. obtains, upon isolation, a dyestufl' similar to that inExample 1, but dyeing cotton a redder shade of blue. This product is soluble in. concentrated sulfuric acid to a reddish In the form of its free acid it corresponds most probably to the followingformula: i

SQaH.

Example 5 i If instead of coupling the diaizo-disazo body, producedin Example 1, to2-phenylamino-5-naphthol-7-sulfonic acid it is coupled to 343parts of 2-benzoylamino-5-naphthoLZ-sulfonid acid dissolved in 5000 parts ofwvater and 1000 parts of soda ash, the

isolated dyestui'f thus produced. dyes, cotton a greener shade of blue than that in Example 1. This product is soluble in concentrated-sulfuric acid to a deep reddish blue solution. In the form of its free acid it corresponds most probably to the foliow ing general formula:

great number general propreplacing the In an analogous manner a of other dyestuffs of similar erties! may be prepared by various components mentioned in Example 1 by their various equivalents as specified at the beginning of this specification. Thus, insteadjof starting with; aniline-disulfonic acid, We mayuse various other. aryl-aminesulfonic acids, for instance: 0-, m-, or

p-aniline-sulfonic acids; the halogen-aniline sulfonic acids; the anisidine-sul'fonic acids; the xylidine sulfonic acids; the various alpha and beta-naphthylamineanonoor poly-sultonic acids; the various amino na )hthol sulfonic acids and the like. dimethoXy-aniline, other dialkoxy anilines Instead of. 2,5-

such as 2,5 diethoxy aniline or 2,6 dimethoxy-aniline maybe used, provided the position para to the amino group is free,

Instead of coupling first to the dialkoxyaniline and then to Cleves acid, we may couple first to Cleves acid and then 'rediazotize and couple to the dialkoxy-aniline. We may also use the. dialkoXy-aniline vided the entire molecule contains a sufficient number of S0 11 groups to render the same Water-soluble to a satisfactory degree. As.

Gleves acid, We may use either the 1,6- or 1,7 -naphthylamine sulfonic acid, or a mixture of the two. The amino group in the end component may be free or substituted by various alkyl, aryl,haralliyl or acidyl radicals; such as; methyl, ethyl, phenyl, acetyl, benzoyl, and the like. Moreover, the azole derivatives of J-acid may be used, for in i as both second and third component, prostance, phenyl-l,2 -naphthimida2ole- -hydroify 7-sulfonic acid.

Other variations and modifications are In the claims below it should be undernot only in substance, but also in whatever state they exist when applied to material dyed,,printed, or pigmented therewith.

We claim as our invention:

1. The process of preparing azo dyestuffs which comprises diazotizing an aryl-amine of the benzene or naphthalene series, cou

pling to a component of the group consisting of dialkoXy-aniline having a free para position and Cleves acid, rediazotizing, coupling to the second member of said group or again to d'iallroXy-aniline, rediazotizing and coupling to a 2-amino-5-naphtholfi-sulionic acid compound.

2. The process of preparing azo dyestuffs, which comprises diazotizing aryl-amine of the benzene or naphthalene seri pling to a dialkoXy-a. ine, in and coupling to a dialkoxy-aniline, ieuiazotizing and coupling to a Q-amino-h-naphthol- 7-sulfonic acid compound.

3. The process of preparing azo dyestnfi's, which comprises diazotiz g of the benzene or naphthalene series. coupling to dialkoXy-aniline. rediazot'ting and coupling to a Cleves acid, rediazot g and coupling to 2a:nino5-naphthol-i -sul tonic acid compound.

4. The process of preparing azo dyestuffs,

which comprises diazotizing an aryl-amine of the benzene or naphthalene series, coupling to a Cleves acid, rediazotizing and coupling to a dialkoxy-aniline, rediazotizing and coupling to a 2-amino5-naphthol-7- sulfonic acid compound.

5. In the process of preparing an azo dysstufl, the step which comprises diazotizing a compound of the following probable general formula: Y

in which R, is an aryl radical of the benzene or naphthalene series which may be further substituted by substituents of the group consisting of alkyl, halogen, hydroxy, alkoXy, and sulfonic acid and in which one of the members R and R is a dialkoXy-benzene radical while the other is a naphthalene sulfonic acid radical or in which both R and R are dialkoxy-benzene radicals. coupling to a compound selected from the group comprising Q-amino-5-naphthoL'T-sulfonic acid and its N-allql, aryl, aralkyl, acidyl or azole derivatives.

6. In the process of preparing an azo dyestuil, the step which comprises diazotizing a compound of the following probable general formula:

I O-alky1 O-alkyl in which R is an aryl radical Ofllll b benzene or naphthalene series which may be further. substituted by substituents of the group consisting of alkyl, halogen, hydroxy, al-

koxy, and sulfonic acid, and coupling to compound having in the form of its free acid the followlng probable general formula:

I OH

in which R is a hydrogen atom or an alkyl, aryl, aralkyl, or acidyl radical.

7. In the process of preparing an azo dyestufi, the step which comprises diazotizing a compound of the following probable general formula:

in which R is an aryl radical of the hen zene or naphthalene series which may be further substituted by substituents of the group consisting of alkyl, halogen, hydroXy, alkoxy, and sulfonic acid, and coupling to a compound having in the form of its free acid the following probable general formula:

in which R is a hydrogen atom or an alkyl, aryl, aralkyl, or acidyl radical.

8. In the process of preparing an azo dyestuff, the step which comprises diazotizing a compound of the following probable general formula:

I O-alkyl (m V in which R is a hydrogen atom or an alkyl, aryl, aralkyl, or acidyl radical.

9. As new products of manufacture. dyestulls having in the form of their free acid the following general formula:

wherein R is an aryl radical of the benzene or naphthalene series which may be further substituted by substituents of the group consisting of alkyl, halogen, hydroxy, alkoxy, and sulfonic acid; wherein one of the members R and R is a dialkoXy-benzone radical while the other is a naphthalene sulfonic acid radical or wherein both its and R are dialkoxy-benzene radicals; and wherein It; stands for the radical of :1

y acid 301111Cl, said dyestuffs being soluble in sulfuric acid with greenish blue to reddish blue colors, and dyeing cotton directly in blue shades.

10. As new products of manufacture, dyestuffs havin in the form of their free acid the following general formula:

wherein R is an aryl radical of the benzene or naphthalene series whlch may be further substituted by substltuents of the group conhydrogen or radical.

12. As new products of manufacture, dyestufis having in the form of their free acid an alkyl, aryl, aralkyl, or acidyl the following general formula:

, H Oalkyl NEPR O-alky1 H 14:. As a new product of manufacture, a dyestuif having in the form of its free acid the following formula:

sisting of alkyl, halogen, hydroxy, alkoxy, and sulfonic acid and R representshydrogen or an alkyl, aryl, aralkyl, or acidyl radical.

11. As new products of manufacture, dyestulfs having in the form of their free acid the following general formula:

wherein R is an aryl radical of the hem zone or naphthalene series which may be further substituted by substituents of the group consisting of alkyl, halogen, hydroxy, alkoxy, and sulfonic acid and R represents said dyestulf bein soluble in concentrated sulfuric acid with a deep navy blue color, and dyeing cotton directly in greenish blue shades.

In testimony whereof, we have hereunto subscribed our names at Carrollville, in the county of Milwaukee, in the State of Wis consin.

IVAN GUBELMANN. ARTHUR R. MURPHY. 

